Solvent Extraction

Based on separating aqueous phase from organic phase

Used in many separations
U, Zr, Hf, Th, Lanthanides, Ta, Nb, Co, Ni
Can be a multistage separation
Can vary aqueous phase, organic phase, ligands
Uncomplexed metal ions are not soluble in organic
phase
Metals complexed by organics can be extracted into
organic phase
Considered as liquid ion exchangers

9-1

Extraction Reaction
Phases are mixed
Ligand in organic phase complexes metal ion in
aqueous phase
Conditions can select specific metal ions
oxidation state
ionic radius
stability with extracting ligands
Phase are separated
Metal ion removed from organic phase
Evaporation
Back Extraction

9-2

Solvent extraction
Influence of chemical conditions
Solvent
Overall extraction, phase splitting
Metal ion and acid concentration
Phase splitting
Distribution coefficient
[M]org/[M]aq=Kd
Used to determine separation factors for a given metal ion
Ratio of Kd for different metal ions
Distribution can be used to evaluate stoichiometry
Evaluation distribution against change in solution
parameter
* Plot log Kd versus log [X], slope is stoichiometry
Extraction can be explained by complexation
Used to determine complexation constants
Consider all speciation in aqueous and organic phase
9-3

Mechanism
Solvation
Extraction of neutral complex
UO2(NO3)2 forms with TBP
* Equilibrium shifts with nitrate, back extraction into
aqueous at low nitric acid
Ion exchange
Metal ion exchanged into organic phase, ion transfer in
aqueous phase
Use of organic soluble acid
i.e., alkyl phosphinic acid (R2PO2H)
Ion pair extraction
Charged metal complex with extractant of opposite charge
i.e., Quaternary ammonium salt with anionic actinide
nitrate

9-4

(CH3CH2)2O Diethyl ether

9-5

Effect of nitric acid concentration on extraction of

uranyl nitrate with TBP

9-6

Reactions
Tributyl Phosphate (TBP)
(C4H9O)3P=O
Resonance of double bond between P and O
UO22+(aq) + 2NO3-(aq) + 2TBP(org) <->UO2(NO3)2.2TBP(org)
Consider Pu4+
Thenoyltrifluoroacetone (TTA)
O

O
CF3

CF3

Keto

Enol

OH

HO

OH
CF3

Hydrate

9-7

TTA
General Reaction
Mz+(aq) + zHTTA(org) <-->M(TTA)z(org) + H+(aq)
What is the equilibrium constant?
Problems with solvent extraction
Waste
Degradation of ligands
Ternary phase formation
Solubility
9-8

9-9

9-10

9-11

9-12

9-13

Non-ideal behavior
Variation in chemical condition during
extraction
Change in acidity
Extractant saturation
Metal or competing ion
Phase dissolution
Solubility into other phase
Degradation
Third phase formation
9-14

Third phase formation

Brief review of third phase formation

Related prior research
Laboratory methods
Np third phase behavior
Comparison with U and Pu
Spectroscopic observations

9-15

Third Phase Formation

In liquid-liquid solvent extraction certain conditions
cause the organic phase to split
PUREX separations using tributyl
phosphate (TBP)
Possible with future advanced separations

Limiting Organic Concentration (LOC) highest

metal content in phase prior to split
Light phase mostly diluent
Heavy phase extractant and metal rich
Problematic to safety!
9-16

Actinide Third Phases

Light Phase
Heavy Phase

Pu(IV)

Pu(VI)

Np(IV)

Np(VI)

Aqueous
Phase
U(VI)
9-17

Importance to Safety

Increased risk of criticality

Phase inversion
Difficulty in process fluid separations
Carry-over of high concentration TBP to
heated process units
Possible contribution to Red Oil event at
Tomsk, Russia

9-18

Phase Inverted Plutonium

Light Organic
Heavy Organic

Aqueous
Inverted Organic
9-19

Prior Research
Majority of work focused on defining LOC

boundary (reviewed by Rao and Kolarik)

-Effects of temp., concs., acid, diluent, etc.

Recent work on possible mechanisms
-Reverse micelle evidence from neutron
scattering (Osseo-Asare; Chiarizia)

-Spectroscopic studies -UV, IR, EXAFS

(Jensen)
9-20

Reverse Micelle Theory

Possible Reverse Micelle

Classical Stoichiometry

UO22+ + 2NO3- + 2TBP

UO2(NO3)2 2TBP

9-21

Role of the Metal

LOC behavior well known for U(VI), U(IV), Pu(IV),
and Th(IV)
Little data available on Pu(VI)
No data on any Np systems
Mixed valence systems not understood

9-22

Mixed Systems
Observed effect of Pu(VI) in HPT vs. C12
Large impact of presence of Pu(VI) in HPT
-Indications heavy phase enriched in Pu(VI)
Opposite found with U(VI) inhibiting phase
separation in U(IV) system (Zilberman 2001)
Suggests possible role of trinitrato species
AnO2(NO3)39-23

Neptunium Study
Unique opportunity to examine trends in the
actinides [LOC curve for U(IV) vs Pu(IV)]
- Effective ionic charge
- Ionic radii
- Stability constants for trinitrato species
Never been investigated
Ease of preparing both tetravalent and
hexavalent nitrate solutions

9-24

Neptunium Methods
Worked performed at Argonne
National Laboratory, Argonne, IL
Stock prepared from nitric acid
dissolution of 237Np oxide stock
Anion exchange purification
-Reillex HPQ resin, hydroquinone (Pu
reductant), hydrazine (nitrous
scavenger)
Np(IV) reduction with hydrogen
peroxide reduction
Np(VI) oxidation with concentrated
HNO3 under reflux

Np(IV) nitrate

9-25

Np(VI) nitrate salt

LOC Behavior
Np(VI) near linear
Np(IV) slight parabolic
Appears between linear U(IV) and
parabolic Pu(IV)
Both curves similar resemblance to distribution
values Purex systems
Suggests possible link with metalnitrate
speciation

9-26

Np Third Phase Boundaries

0.30

Np(IV)
Np(VI)

LOC, M

0.25

0.20

0.15

0.10

0.05

7
HNO3, M

10
9-27

Comparison with Other Actinides

LOC in 7M HNO3 / 1.1M TBP/dodecane 20-25 C, M
An (IV)

An (VI)

U
0.08
(Wilson 1987)

Np
0.15

Pu
0.27
(Kolarik 1979)

No 3
(Chiarizia 2003)

0.17

0.10

9-28

Organic Nitric Acid

Balance available TBP and organic H+
Np(IV) = mixture of the monosolvate (TBP
HNO3) and hemisolvate (TBP 2HNO3) species
Np(VI) = hemisolvate

Agrees with literature data on U(VI) and

Th(IV) acid speciations

9-29

Valence Trends An (IV)

General trend = decreasing LOC as ionic radii
increases
Lowest charge density = lowest LOC
Np intermediate between U and Pu
Literature Th(IV) data consistent with trend

9-30

Valence Trends An(VI)

An(VI) = LOC increases as ionic radii decreases
Opposite trend for An(IV), including Th(IV)
Charge density using effective cationic charge and 6coordinate radii
No evidence of correlation with charge density
within error of effective charge data
Oxo group interactions not fully considered

Future work required

9-31

Spectral Study Methods

Look for spectral trends in Np(VI) system
Examined trends for:
-LOC
-Metal loading
-Nitrate loading (using NaNO3)
5 mm quartz cuvette with Cary 5 Spectrometer

9-32

LOC Spectra
Np(VI) 30% TBP / dodecane at LOC
1.0

[HNO3], M

Absorbance

0.8

0.6

4
6
7
8
10

0.4

0.2

0.0
900

1000

1100

Wavelength, nm

1200

1300

9-33

Metal Loading

Absorbance

0.8
0.6

[Np(VI)]org, M
LOC = 0.27
0.18
0.09
0.03

0.4
0.2
0.0
900

1000

1100

1200

1300

Wavelength, nm
9-34

Nitrate Effects
0.9

0.20
-

0.6

4
5
6
saturated

0.15

Absorbance

Absorbance

[NO3], M

0.3

0.10
0.05

0.0
1000

1100

1200

Wavelength, nm

Aqueous

1300

0.00
1000

1100

1200

1300

Wavelength, nm

Organic
9-35

[H+] = 4M, [Np(VI)] = 0.03M

Valence Scoping Experiments

Examined various mixes of Pu(IV)/Pu(VI)
Solutions prepared by method of slow addition
of concentrated HNO3 to heated syrupy Pu
nitrate solution
Use UV-Vis peak analysis for determination of
initial aqueous composition
Perform mole balance on aqueous phase before
and after contact for organic content of each
valence species (some samples)
9-36

Spectrum Mixed Valence Phases

9-37

Third phase conclusions

Third phase behavior measured in Np

LOC trends consistent with U and Pu
Np(IV) LOC trends with charge density
No clear correlation for Np(VI)
Spectroscopic evidence suggests possible role of
trinitrato species in third phase

9-38

Basic decay equations

The radioactive process is a subatomic change within
the atom
The probability of disintegration of a particular atom
of a radioactive element in a specific time interval is
independent of its past history and present
circumstances
The probability of disintegration depends only on the
length of the time interval.

Probability of decay: p=Dt

Probability of not decaying: 1-p=1- Dt
9-39

StatisticsofofRadioactive
Radioactive Decay
Statistics
Decay
1-p=1-Dt=probability that atom will survive Dt
(1- Dt)n=probability that atom will survive n intervals of Dt

nDt=t, therefore (1- Dt)n =(1- t/n)n

Since limn(1+x/n)n=ex, (1- t/n)n=e-t, the limiting value.
Considering No atoms, the fraction remaining unchanged
after time t is N/No= e-t

N=Noe-t
where is the decay constant

9-40

Radioactivity as Statistical
Phenomenon
Binomial Distribution for Radioactive Disintegrations

probability W(m) of obtaining m disintegrations in

time t from No original radioactive atoms
No!
W (m )
p m (1 p ) N o m
( N o m )! m!

probability of atom not decaying in time t, 1-p, is

(N/No)=e-t, where N is number of atoms that survive
in time interval t and No is initial number of atoms
Time Intervals between Disintegrations

probability of time interval having value between t

9-41
and t+d:
P(t )dt N oe N t dt
o

 Average Disintegration Rate

W (r )
where 1-p=q

n!
p r q n r
( n r )! r !

np r 0 rW ( r ) r
r n

for radioactive disintegration--if n=No and p=1e-t--average number M of atoms disintegrating

in time t is M=No(1-e-t); for small t, M=Not
and disintegration R=M/t=No , which
corresponds to -dN/dt=N
Expected Standard Deviation

s N o (1 e t )e t Me t
Since in counting practice t is generally small, s M

M is number of counts
Relative error = s-1

9-42